Detergent composition



Patented Oct. 23, 1951 DETERGENT COMPOSITION Jay C. Harris, Dayton, Ohio, and Milton Kosmin, Los Angeles, Calif., assignors to Monsanto Chemical Company, a corporationof Delaware No Drawing. Application October 17, 1947,

Serial No. 780,576 4 13 Claims. 1

The present invention relates to the solution Of the old problem of grease-ball formation in the field of washing or detergency and the method of solving this problem by means of particular compositions of matter.

An object is to provide washing compositions of unusually high detersive efficiency, particularly for use in areas having very hard water.

It is well known in the problem of cleansing clothes and industrial materials that grease balls or soap balls may be formed under a wide variety of circumstances. Laundries are well aware of the problem of deposition of such concentrations of greasy material, generally designated as grease balls, which cause unsightly, spotty stains upon the material being washed. The difliculty is described by F. H. Guernsey in an article in the American Dyestufi Reporter, 15, pp. 422-425.

The present invention sets forth a solution to the old problem of grease ball formation by means of a new and difl'erent composition adapted to provide excellent detergency, while avoiding the formation of grease balls. Another object of the present invention is to provide such a cleansing composition as may be used in the modern closed' body, semior fully automatic, washing machines in which the formation of foam or suds must be greatly restricted. This restriction is desired for the reason that such washers, which are automatic in the addition of a fixed quantity of water, as well as in the, control of the wash cycle and temperature, provide only a limited space for the swirling body of liquid and clothes, so that there cannot be an excess of foam. If too much foam is formed by the detergent, it will leak out of various parts of the automatic washing machine. Furthermore, the foam actually blankets the drop or mechanical washing effect produced by rotation of the cylinder.

The laundering industry has endeavored to solve the problem of grease balls by the use of excessive and uneconomical amounts of soap, or

soap and lime-soap regenerating agents. However, this cannot be considered to be a commercially practicable solution to the present problem. Furthermore, in washing oily or greasy fabrics, such as overalls or oily cloths which must be cleaned in certain industrial operations, even this expedient of excess soap is not effective.

The presence of metallic ions in water as may occur in certain industrial applications, or the employment of hard water such as is common in large areas extending across many states are also militating factors against the solution of the grease ball problem by means of soap alone. The present invention, in providing a detergent composition which may be in essence non-ionic, allows the use of hard water which would render ordinary washing operations practically impossible.

The invention is concerned with detergent mixtures of particular emciency which may be made by the combination of certain ethylene oxide condensation products. We have found that ethylene oxide condensation products with tall oil or other abietic acid sources, when used in combination with condensation products of ethylene oxide with certain mercaptans, provides the optimum composition to eliminate grease balls in washing operations. Ethylene oxide may be condensed with these materials either in a simultaneous process or by individual reactions followed by blending of the condensation products. In either circumstances, the present superior results are obtained. The ethylene oxide may be introduced in various ratios to obtain condensation products ranging from equivalent ratios to the range of about 40 moles permoleof said mercaptan, and 3.4 to 34 moles of the abietic acid product such as rosin or tall oil. Variation in this respect will permit particular objects to be accomplished in such fields of application as may be desired; preferred ranges are set out in greater detail below.

The present compositions are produced by the use of ratios of about 10% to 40% of the mercaptan-ethylene oxide condensation product in relation to the total of the same with that resulting from the reaction with abietic acid or products containing the same, such as rosin, rosin oil or tall oil. This ratio may also be defined as 1.5:1 to 951 of the abietic acid product with respect to the mercaptan product. A preferred range in the same relationship is 3:1 to 6:1.

It is also contemplated in the present invention that the above concentrates of non-ionic detersive materials may be used in conjunction with alkali metal phosphate salts and other alkaline builders or cleansing agents, as well as with adjunct materials as are described below for the purpose of providing non-depositing cleansing materials to avoid the formation of grease balls.

In order that the invention may be clearly understood and readily carried into efiect, some practical methods of carrying out the process according to the invention will now be described in somewhat greater detail by way of example.

EXAMPLE 1 A unitary composition was produced in which the-abietic acid source and the mercaptan were mixed before condensation with ethylene oxide. The charge was 129.5- parts by weight of crude tall oil and 43.2 parts of technical, tertiary dodecyl mercaptan. To this mixture was added 3.5 parts of sodium hydroxide as a catalyst. The mixture was heated, and ethylene xide addition started to keep the temperature at -155 C. by means of a liquid bath. Heat evolution was vigorous and cooling was necessary in the first part of the reaction. After the initial vigor of the reaction had subsided, the flow of ethylene oxide was increased until a total of 276.3 parts by weight had been 3 absorbed. The product was a solid of flrm sellike consistency.

The surface tension of dilute solutions of the above non-ionic composition was found to be lower than that of the tall 011 condensation product, providing an eflective detergent. This unitary condensation product possesseddetersive action per se, and was also adaptable to formulation with builders such as is conventional in providing commercial products. In particular, the mixtures or combinations of condensation products made it possible to wash clothing without producing any grease ball stains.

Variations studied in carrying out other preparations showed that the amount of ethylene oxide could be varied in the range of 3.4 to 34 moles per mole of abieticv acid acceptor in the initial mixture (0.5 to 5.0 weight per weight ratio), although the preferred range was 6.8 to 20.4 moles (1.0 to 3.0 weight ratio). Similarly the ethylene oxide condensed with the mercaptan present may vary from 1.0 to 40 moles per mole of mercaptan acceptor (0.28 to 9.1 weight ratio), the preferred range being 6.6 to 11.0 moles of ethylene oxide (1.5 to 2.5 weight basis). In these and the other compositions of our invention the tall oil is replaceable by abietic acid or rosin and the mercaptan is aliphatic, i. e., straight chain, per se, or cycloaliphatic. In the preferred embodiment the mercaptan may be highly branched, as for example, a tertiary mercaptan of 8 to 18 carbon atoms as described in greater detail below.

EXAMPLE 2 applied to keep the temperature of the reaction mass at about 125 C. The heat evolution was controlled by the rate of feed of ethylene oxide. The addition of this compound was accelerated after the initial vigor of the reaction had subsided. Ethylene oxide was added until about 84 pounds (1.91 moles) had been taken up, after which the reaction mixture was cooled and poured into cooling pans. Tests of the final products. when combined with the tall oil-ethylene oxide condensation products, gave the results summarized below in the'present application to obtain a powerful non-ionic wetting agent and deter-gen of excellent solubility in water.

Various mercaptans may be employed in the present process, including the aliphatic and cycloaliphatic mercaptans disclosed in U. S. Patent N 0. 2,205,021, as well as the branched chain mercaptans described in application Serial No. 718,133, filed by one of us. Therefore, iso compounds and tertiary compounds are both suitable. In this relationship the branched-chain forms of hexyl, heptyl, cctyl, decyl, dodecyl, tetradecyl, hexadecyl. octadecyl and arachyl mercaptans are preferred. By a branched-chain mercaptan we mean a compound having an SH group linked to the carbon atom of a hydrocarbon molecular structure which exhibits a plurality of terminal groups. For this reason both secondary and tertiary types may be utilized, although we prefer that the ramifications be as extensive as possible, generally characterized by the term ramulose. However, the individual branched-chains should comprise aliphatic and cycloaliphatic chains in contrast to 5 aromatic types. The total number of carbon atoms present in each mercaptan molecule before condensation may range from 6 to 20, although the preferred compounds are the 8 to 18 carbon atom types.

The preferred branched-chain mercaptans which are used may be derived from petroleum aliphatic sources such as is-shown in U. S. Patent 2,392,555. It is known in the art of olefin pol vmerization to make liquid polymers of the isol5 octene type having from 8 to 18 or more carbon atoms. Such polymers are characterized by pronounced branching of-the carbon skeletons of the molecule, and when reacted with hydrogen sulflde to form mercaptans, are predominantly of 20 the tertiary type. Furthermore, it is possible to effectuate even greater branching of the polymer feed stock, together with a net shift of the reactive point to a central location of themolecules, before mercaptan formation, by utilizing a reforming or isomerizing reaction to obtain substantially complete consolidation in type to tertiary structures of the reacting molecules.

A sample of the tertiary dodecyl mercaptan feed stock used in the ethylene oxide condensations was subjected to distillation by the ASTM method carried out at 5 mm. absolute pressure. Th material showed an initial boiling point of 172 F. and a 95% overhead at 207 F. The mercaptan content was found to be 96.8%, and a typical sample had an average molecular weight of 193.3, specific gravity (60/60 F.) of 0.8713, and was found by chemical analysis to contain 15.9% SH sulfur, corresponding to a mono-mercaptan. As shown by the chemical bonding required to achieve the present branched-chain mercaptanalkylene oxide compositions, mono-mercaptans are predominantly used in the instant compositions.

As a catalyst in the condensation reaction, whether employing a mercaptan, an abietic acid product, or mixtures, we prefer to use the hydroxide of an alkali metal such as sodium or potassium hydroxide. However, the carbonates may also be used. Apparently, the basic catalyst forms an intermediate compound with the mercaptan or hydroxyl reacting abietic acid, and may then enter into chain formation. However, it has been observed that the reaction product gives a neutral reaction in aqueous solution, so that any basicity is apparently lost in the final condensation product. Hence, the invention is not to be limited as'w any theory since the above is offered only by way of explanation regardless of its seeming validity.

The individual condensation products derived from ethylene oxide with tall oil or abietic acid products generally were produced in the Example 11 compositions by a separate process prior to blending of such materials with the mercaptan condensation product. The individually produced products were then blended to obtain the final combination which possesses the unique grease ball preventive capacity.

In carrying out such individual operations the compounds may be produced by reacting abietic acid, or products containin the same, such as rosin, rosin oil, or tall oil with ethylene oxide in amount such that at least 0.5 part, but less than 5.0 parts by weight of ethylene oxide per part of abietic acid (3.4 to 34 moles per mole) are con- I densed. Such intermediate condensation compounds thus obtained may be combined with the mercaptan condensation product described above. A preferred range of ethylene oxide concentration is 1.0 to 3.0 parts per part of the ethylene oxide acceptor (6.8 to 20.4 mole ratios).

Ordinary rosin or colophony contains abietic acid or abietic anhydride in substantial amounts. There may also be present l-pimaric and dpimaric acid. Abietic acid is considered to have the empirical formula CzoHaoOa and is a monocarboxylic acid related structurally to phenanthrene. The form of abietic acid occurring in ordinary rosin may, upon treatment with acetic acid or with alkalies, be converted into Steel's abietic acid. Tall oil, by reason of the treatment of the original wood with alkali, contains abietic acid in the form of Steel's acid. This particular acid is unstable and readily oxidizable. It maybe subjected to a disproportionation treatment to yield a product containing resin acids ofthe formulae, CaoHaaOz and C2oHa202, which are known as dehydroabietic acid and dihydroabietic acid, respectively.

The present compositions, when made by the present process may result from the reaction of abietic acid products such as the acid per se or sources containing the same including Steele's acid, dehydroabietic acid, dihydroabietic acid, rosin, rosin oil or tall oil. This condensation product is then combined with the above mercaptan composition.

Thus, it is seen that the present invention sets out new and different compositions. These find application in a large number of industrial processes especially in those relating to the treatment oftextiles, leather and other fibrous materials. The excellent wetting out properties resulting from the low surface tension, together with the substantial absence offoam,.of the present products in very low concentrations renders them particularly useful. Applications to industrial processes include their use as textile adjuvants in the dye bath, in the preparation of aqueous solutions, emulsions or suspensions of compounds which are in themselves sparingly soluble, for making dressings containing magnesium sulfate, for enhancing the efficiency of carbonizing and mercerizing liquors to wet the fabric and as surface active agent in dry cleaning operations and the like. In all of these uses, the property of grease ball elimination is an essential factor inherent in the combination set out above.

Table I TEST DATA OF MIXTURES Ethylene oxide-tall oil; Ethylene oxide-t.-dodecyl mercantan (L72 ratio) Example 1 joint condensation product 'Ietrnsodium nyrnnhospliaic Sodium triphosphate Sodium scsquicarhonate.

Reference to the test data of Table I indicates that the mixtures of the tall oil-ethylene oxide condensation products and dodecyl mercaptanethylene oxide condensation products are all possessed of superior detergent qualities. be noted that the particular compositions of the invention (A, B, C and D) which have been tested show detergencies well over against the reference standard, Gardinol WA, which is the so dium salt of a sulfated lauryl alcohol. Consequently, all of these new compositions are superior to this reference material, which is a typi cal commercially available synthetic detergent. Sample E is representative of the prior art compositions.

The presence or absence of grease balls is ordinarily detected by visual examination of the washed fabric. In the table above the absence of grease balls is indicated by a minus sign, their presence by a plus sign. The method of testing was based upon extreme conditions which would produce grease balls under a specifled set of test situations. This was done with standard prepared fabrics which had been pretreated or soiled with one of the following test mixture compositions:

1. Conventional lime soap, together with an oily medium of cottonseed oil, white mineral oil and petrolatum.

2. Zinc stearate and baby oil (a refined white mineral oil).

3. White medicinal mineral oil, cottonseed oil, petroleum jelly, corn oil, and purified lanolin.

It will be observed that the compositions containing the branched-chain mercaptan-ethylene oxide condensation products were free of grease balls. Additional test data have shown that this result is obtained when one part by weight of mercaptan-ethylene oxide condensation product is mixed with from 1.5 to 9 parts of the tall oilethylene oxide product. Thus, of the total ethylene oxide condensation product present in the detergent, from 10% to 40% by weight should be the mercaptan-ethylene oxide product.

The content of combined ethylene oxide in the individual condensation product is also subject to some variation. The above described results are obtained over the range of from 0.28 part to 9.1 parts by weight of combined ethylene oxide per part of mercaptan acceptor, and 0.5 to.5.0 parts of ethylene oxide per part of the abietic acid type acceptor in the combination.

The condensation products may be employed as detergents in the general proportion of 1.511 to 9:1 of the tall oil product with respect to the mercaptan condensation product. However, a particularly effective region of compositions has been found to fall in the range of 3:1 to 6:1 ratios of the tall oil condensation product with respect to that derived from mercaptans. In the production of such detergent compositions we may carry out the ethylene oxide condensation either on individual batches of the tall oil and of the tertiary mercaptan, respectively, or provide a unitary composition in which said tall oil and mercaptan are first premixed and then subjected to the ethylene oxide condensation. Either method provides the desirable effect achieved by the combination of such condensation products The particular process which we may employ is more a matter of convenience, since either process provides the final product having the above ratio of the constituents.

Another factor realized by the provision of mixtures of the herein-disclosed ethylene oxide condensation products is the lowering of surface It will tension. It is well known in the theory of detergency that an agent having a lower surface tension is of great value in the washing process, since it enables an emulsion or suspension to be formed more easily for the removal of oily particles which are-generally associated with various soils and stains. Thus. the mixtures of such condensation products have been found to result in a low surface tension value. This feature, while it is apparently fundamental in the functioning of the detergent compositions, is, however, not the sole cause of the newly discovered property of grease ball elimination, since such result is apparently achieved as the concomitant function of several variables. Thus, the systems created by the use of our present-mixtures allow emulsiflcation to occur for the purpose of soil removal, even though the emulsions or suspensions so produced are less stable than are possible with substances of greater surface activity.

It might be supposed that the function of surface tension reduction and grease ball elimina- WA and found to be a sodium salt of a sulfated fatty alcohol.

For producing the present grease ball eliminating compositions as commercial formulations, the

ethylene oxide condensation products described above may .be mixed with any alkali, e. g., sodium or potassium phosphate. Suitable phosphates are tion might be accomplished by the use of any conventional wetting agent. However, there is more to the problem of grease ball elimination thanthe factor of surface tension as is shown, for example, by the interfacial tension measurements. The interfacial tension values measured between oil and an aqueous solution of the particular detergent composition is the best indication ofpotential emulsiflcation. However, in studying the range of mixtures of the two ethylene oxide condensation products, it was noted that this factor of interfacial tension did not change materially from the high level characteristlc of the individual components. HOWGVGI,'

the function of grease ball elimination appears to be related to surface tension insofar as the particular claimed range of mixtures solves the grease ball problem while providing lower surface tension values. It may also be that some not presently recognized specific surface change occurs to reduce grease ball formation in the narrow range of mixtures of the ethylene oxide condensation products.

Another factor in the elimination of grease balls in detergents derived from ethylene oxide condensation products is the problem of compatibility. It was found, for example, that when the conventional wetting agents, such as sulfonated alkylbenzene, were added even in double the usual proportion. the surface tension of the solution of the final detergent was reduced only slightly and that the detergency of the final product was practically unchanged, or if changed at all amounted only to a dilution effect. Furthermore, such mixtures still gave grease balls in clothes-washing tests.

The data summarized in Table I show the eflicacy of the present mixtures of ethylene oxide condensation products as detergents. The data of this table express detergency as measured by the standard washing tests with a Launderometern This method of testing is, summarized below, and is more completely described in an article by Jay C. Harris in a series of articles in Soap and Sanitary Chemicals for August and September 1943, and also in another article by the same author, "The Evaluation of Surface-Active Agents in the Bulletin of the American Society of Testing Materials, May, 1946. The detersive effectiveness of each sample of Table I was compared with that of a commercially available synthetic detergent known to the trade as Gardinol any of the polyphosphates, such as crystalline sodium tripolyphosphate, NasPsOm. or sodium tetraphosphate, NaaP4Ou, or fused or sintered products approximating these compositions. Sodium hexametaphosphate, sodium pyrophosphate and particularly the tetrasodium pyrophosphate, Na4P201, may be used, these products being preferred in the anhydrous form. The alkali metal orthophosphates may also be employed. Typical members of thisgroup are trisodium orthophosphate, disodium orthophosphate or monosodium orthophosphate. The above products may be used as such or in mixtures, or in admixture with other inorganic water-soluble salts such as soda ash, sodium sulfate, sodium berate, etc., such as are common in the art. A preferred adjunct to be used with the phosphate is the sodium sesquicarbonate or its molecular equivalent as a mechanical mixture. Thus, the carbonate may vary somewhat from the stoichiometric ratio.

Colloidal carbohydrate material such as starch, methylcellulose or carboxy methylcellulose are advantageously added to mixtures of the said condensation product with or without alkali metal phosphate. The amount of the carbohydrate material added may vary overwide limits. The starch employed is the ordinary corn or potato starch and maybe employed inthe form commonly known as pearl starch or in the finely powdered form. It may be employed in amounts up to 80% by weight of the mixture. Dextrin materials such as are ordinarily derived from starch by various degradation processes may also be used.

When methylcellulose is employed in this relationship it is utilized in its low viscosity form. The commercial product, designated as Methocel 15 C. P. S. is suitable, for example. Carboxymethylcellulose is also a desirable additive to the present built compositions. This compound is described in the Journal of Industrial and Engineering Chemistry, vol. 37, page 942. The material is available in various forms. The type \xhich is soluble in alkalies and which is known as the "low substituted" type is preferred for compositions adjusted to an alkaline pH, as would generally be desirable. Methylcellulose or carboxymethylcellulose is generally employed in relatively minor amounts, from 0.1% to 5% by weight of the mixture.

The efficiency of the present formulations-in eliminating grease balls in detergent applications may be considerably improved by mixing the Desirably the. three or' more thermore, since the mercaptan-ethylene oxide reaction products are pasty materials of low melting point, they may preferably be mixed with fillers 'such as sodium chloride, bentonite, kieselguhr, etc. in proportions such as will give a dry, powdery product.

Suitable dry and free-flowing products may contain the following ingredients in-per cent by weight:

Exmen: 3

Tertiary tetradecyl mercaptan-ethylene oxide condensation product of the type produced in Example 2 12 -Tall oil-ethylene oxide condensation product of the type produced in Example 2 Tetrasodium pyrophosphate, anhydrous 40 Sodium sesquicarbonate 40 The above ingredients, the condensation products being first melted, are mixed together in a dry mixer until a free-flowing, dry powder is produced. This product shows excellent detergency, particularly in hard water, and is characterized by especially eflicient'wetting action, without the formation under any normal circumstances of ';-..grease ball formation.

The dry. powdery form of our improved grease ball eliminating detergent may be packaged and sold as such for. use in automatic washing machines. proportioned by means of automatic feeding or proportionating equipment. In this relationship,

' we may also market such packages in unit sizes which are adapted for home washings, so that no further measurement is necessary, and the 1 entire unitary package may be used in an automatic washing machine.

A combination peculiarly suitable for home washing purposes, as described above, was compounded as shown in:

EXAMPLI: 4

. Parts Ethylene oxide, condensation product with tall oil, 1.6 ratio -20 Ethylene oxide condensation product with tertiary dodecyl mercaptan, 1.8 ratio 2-8 Starch -25 Sodium sesquicarbonate 15-25 Tetrasodium pyrophosphate -50 Qarboxymethylcellulose 0.5-3.0

and fillers employed in our compositions, both as described above and as is conventional in the se of related materials in the art. such additives should not include the ordinary fatty acid soaps.

For this purpose it may be conveniently 10 the same time overcome th tendency of prior art materials to form grease balls.

Certain portions of the present disclosure are the subject matter of other patent applications:

Serial No. 718,133, filed December 23, 1946; Serial No. 637,096, filed December 22, 1945, now abandoned; Serial No. 637,079, filed December 22, 1945, now abandoned; and by either or both of the present inventors.

It should be understood that the present invention is not limited to the specific procedure and compounds hereinbefore disclosed, but that it extends to all equivalent methods covered by the generic and specific features of our invention herein described and all statements of the invention which, as a matter of language, might be said to fall therebetween.

Letters Patent of the United States is:

The reason for this in the sudsing tendency ex- 1. A detergent composition which prevents the formation of grease balls during washing, said detergent composition comprising essentially a mixture of the condensation product of one mole of tall oil with 3.4 to 34 moles of ethylene oxide in combination with a condensation product of one mole of an aliphatic mercaptan, having from 6 to 20 carbon atoms condensed with from 1 to 40 moles of ethylene oxide, said respective condensation products being present in proportion by weight of from 1.5:1 to 9:1.

2. A detergent composition which prevents the formation of grease balls during washing, said composition comprising essentially the condensation product of one mole of tall oil with 6.8 to 20.4 moles of ethylene oxide in combination with the condensation product of one mole of tertiary dodecyl mercaptan with 6.6 to 11.0 moles of ethyl ene oxide, said respective condensation products being present in proportion by weight in the range of from 3:1 to 6:1.

3. A detergent composition which prevents the formation of grease balls during washing, said detergent composition comprising essentially the composition of claim 1 to the extent of 20% by 4. A detergent composition which prevents the formation of grease balls during washing, said detergent composition comprising essentially the following ingredients in parts by weight:

Part-s Combination condensation product of claim 1- 20 Starch 40 Tetrasodium pyrophosphate 40 5. A detergent composition which prevents the formation of grease balls during washing, said detergent composition comprising essentially the composition of claim 2 to the extent of 20% by weight in combination with:

Per cent Tetrasodium pyrophosphate 40 Sodium sesquicarbonate 40 6. A detergent composition which prevents the formation of grease balls during washing, said detergent composition comprising essentially the following ingredients of parts by weight:

' Parts Combination condensation product of claim 2 20 Starch 40 Tetrasodium pyrophosphate 40 11 7. A detergent composition which prevents the formation of grease balls during washing, said de-' tergent composition consisting of the following ingredients in parts by weight:

Parts Ethylene oxide condensation with tall oil (1.6:1 weight ratio) -20 Ethylene oxide condensation with tert.-

8. A detergent composition which prevents the formation of grease balls during washing, said detergent composition consisting of the following ingredients in parts by weight:

Ethylene oxide condensation product with tall 011 (1.6:1 weight ratio) Ethylene oxide condensation product with detergent composition consisting of the following Parts ingredients in parts by weight:

12. A detergent composition which prevents the formation of grease balls during washing, said detergent composition comprising essentially the combination of an ethylene oxide condensation product with a molal proportion of from 3.4 to 34 moles of ethylene oxide per mole of a member selected from the class consisting of tall oil, rosin, abietic acid and mixtures thereof, and an ethylene oxide condensation product with a molal proportion of from 1 to 40 moles of ethylene oxide per mole of a mercaptan selected from the class consisting of aliphatic and cycloaliphatic mercaptans having from 8 to 18 c bon atoms, said respective condensation product eing present in the weight ratio of from 1.5:1 to 9:1.

13. A detergent composition which prevents the I formation of grease balls during washing, said tert.-dodecyl mercaptan (1.8:1 weight ratio) 5 Starch 19 Sodium sesquicarbonate 20 Tetrasodium pyrophosphate 40 Carboxymethylcellulose 1 9. A detergent composition which prevents the formation of grease balls during washing, said detergent composition comprising essentially the condensation product of one part of tall oil and 1.6 parts by weight of ethylene oxide, in combination with the condensation product of one part of tertiary dodecyl mercaptan with 1.8 parts by weight of ethylene oxide, said respective condensation products being present proportionally lntherange of321to6z1.

10. A detergent composition which prevents the formation of grease balls during washing, said detergent composition comprising essentially the composition of claim 9 to the extent of 20% by weight in combination with:

Per cent Tetrasodium pyrophosphate 40 Sodium sesquicarbonate 40 11. A detergent composition which prevents the formation of grease balls during washing, said detergent composition comprising essentially the combination of an ethylene oxide condensation product with a molal proportion of from 6.8'to 20.4 moles of ethylene oxide per mole of tall oil, and an ethylene oxide condensation product with a molal proportion of from 6.6 to 11 moles of ethylene oxide per 'mole of aliphatic mercaptans having from 8 to 18 carbon atoms, said respective condensation products being present in the weight ratio of from 3 :1 to 6:1. JAY C. HARRIS. MILTON KOSMIN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,129,709 Schuette et al Sept. 13, 1938 2,307,058 Moeller Jan. 5, 1943 2,335,194 Nuesslein et al. Nov. 23, 1943 2,469,493 Barker May 10, 1949 FOREIGN PATENTS Number Country Date 469,334 Great Britain July 23, 1937 498,743 Great Britain Jan. 9, 1939 

1. A DETERGENT COMPOSITION WHICH PREVENTS THE FORMATION OF GREASE BALLS DURING WASHING, SAID DETERGENT COMPOSITION COMPRISING ESSENTIALLY A MIXTURE OF THE CONDENSATION PRODUCT OF ONE MOLE OF TALL OIL WITH 3.4 TO 34 MOLES OF ETHYLENE OXIDE IN COMBINATION WITH A CONDENSATION PRODUCT OF ONE MOLE OF AN ALIPHATIC MERCAPTAN, HAVING FROM 6 TO 20 CARBON ATOMS CONDENSED WITH FROM 1 TO 40 MOLES OF ETHYLENE OXIDE, SAID RESPECTIVE CONDENSATION PRODUCTS BEING PRESENT IN PROPORTION BY WEIGHT OF FROM 1.5:1 TO 9:1. 